The present invention relates to novel xcex1-sulfin- and xcex1-sulfonamino acid amides of formula I below. It relates to the preparation of those substances and to agrochemical compositions comprising at least one of those compounds as active ingredient. The invention relates also to the preparation of the said compositions and to the use of the compounds or of the compositions in controlling or preventing the infestation of plants by phytopathogenic microorganisms, especially fungi.
The invention relates to xcex1-sulfin- and xcex1-sulfonamino acid amides of the general formula I 
including the optical isomers thereof and mixtures of such isomers,
wherein
n is a number zero or one;
R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfonyl, C3-C8cycloalkyl, cyano, C1-C6alkoxycarbonyl, C3-C6alkenyloxycarbonyl or C3-C6alkynyloxycarbonyl; C3-C8cycloalkyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12haloalkyl; or a group NR12R13 wherein R12 and R13 are each independently of the other hydrogen or C1-C6-alkyl, or together are tetra- or penta-methylene;
R2 and R3 are each independently hydrogen; C1-C8alkyl; C1-C8alkyl substituted with hydroxy, mercapto, C1-C4alkoxy or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl; C3-C8cycloalkyl-C1-C4alkyl; or the two groups R2 and R3 together with the carbon atom to which they are bonded form a three- to eight-membered hydrocarbon ring;
R4, R5, R6 and R7 are each independently hydrogen or C1-C4alkyl;
R8 is C1-C6alkyl, C3-C6alkenyl or C3-C6alkynyl;
R9 and R10 are each independently hydrogen or C1-C4alkyl; and
R11 is either 
xe2x80x83in wherein
R14, R15, R16 and R17 are each independently hydrogen or C1-C4alkyl,
X is oxygen, sulfur or xe2x80x94NR18xe2x80x94, wherein R18 is hydrogen or C1-C4alkyl, and
A is optionally substituted mono- or polycylic aryl or heteroaryl.
In the above definition aryl includes aromatic hydrocarbon rings like phenyl, naphthyl, anthracenyl, phenanthrenyl, with phenyl being preferred.
Heteroaryl stands for aromatic ring systems comprising mono-, bi- or tricyclic systems wherein at least one oxygen, nitrogen or sulfur atom is present as a ring member. Examples are furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl and naphthyridinyl.
The above aryl and heteroaryl groups may carry one or more identical or different substituents. Normally not more than three substituents are present at the same time. Examples of substituents of aryl or heteroaryl groups are: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, phenyl and phenyl-alkyl, it being possible in turn for all of the preceding groups to carry one or more identical or different halogen atoms; alkoxy; alkenyloxy; alkynyloxy; alkoxyalkyl; haloalkoxy, alkylthio; haloalkylthio; alkylsulfonyl; formyl; alkanoyl; hydroxy; halogen; cyano; nitro; amino; alkylamino; dialkylamino; carboxy; alkoxycarbonyl; alkenyloxycarbonyl; alkynyloxycarbonyl.
In the above definitions xe2x80x9chalogenxe2x80x9d includes fluorine, chlorine, bromine and iodine.
The alkyl, alkenyl and alkynyl radicals may be straight-chain or branched. This applies also to the alkyl, alkenyl or alkynyl parts of other alkyl-, alkenyl- or alkynyl-containing groups.
Depending upon the number of carbon atoms mentioned, alkyl on its own or as part of another substituent is to be understood as being, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the isomers thereof, for example isopropyl, isobutyl, tert-butyl or sec-butyl, isopentyl or tert-pentyl.
Cycloalkyl is, depending upon the number of carbon atoms mentioned, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
Depending upon the number of carbon atoms mentioned, alkenyl as a group or as a structural element of other groups is to be understood as being, for example, ethenyl, allyl, 1-propenyl, buten-2-yl, buten-3-yl, penten-1-yl, penten-3-yl, hexen-1-yl, 4-methyl-3-pentenyl or 4-methyl-3-hexenyl.
Alkynyl as a group or as a structural element of other groups is, for example, ethynyl, propyn-1-yl, propyn-2-yl, butyn-1-yl, butyn-2-yl, 1-methyl-2-butynyl, hexyn-1-yl, 1-ethyl-2-butynyl or octyn-1-yl.
A haloalkyl group may contain one or more (identical or different) halogen atoms, and for example may stand for CHCl2, CH2F, CCl3, CH2Cl, CHF2, CF3, CH2CH2Br, C2C5, CH2Br, CHClBr, CF3CH2, etc.
Where R2 and R3 together with the carbon atom to which they are attached form a hydrocarbon ring the ring corresponds to cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane or cyclooctane
The presence of at least one asymmetric carbon atom and/or at least one asymmetric oxidized sulfur atom in the compounds of formula I means that the compounds may occur in optically isomeric forms. As a result of the presence of a possible aliphatic Cxe2x95x90C double bond, geometric isomerism may also occur. Formula I is intended to include all those possible isomeric forms and mixtures thereof.
Preferred subgroups of compounds of formula I are those wherein
n is one; or
R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, or C1-C4alkylsulfonyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12haloalkyl; or a group NR12R13 wherein R12 and R13 are each independently of the other hydrogen or C1-C6-alkyl, or together are tetra- or penta-methylene; or
R1 is C1-C12alkyl, C2-C12alkenyl; C1-C12haloalkyl; or a group NR12R13 wherein R12 and R13 are each independently of the other hydrogen or C1-C6-alkyl; or
R1 is C1-C4alkyl, C2-C4alkenyl; C1-C4haloalkyl; or C1-C2-dialkylamino; or
R1 is C1-C4alkyl, vinyl; C1-C4haloalkyl; or dimethylamino; or
R2 is hydrogen and R3 is C1-C8alkyl; C1-C8alkyl substituted with hydroxy, mercapto, C1-C4alkoxy or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl; C3-C8cycloalkyl-C1-C4alkyl; or
R2 is hydrogen and R3 is C1-C4alkyl; C3-C4alkenyl or cyclopropyl; or
R2 is hydrogen and R3 is C3-C4alkyl; allyl or cyclopropyl; or
R2 is hydrogen and R3 is isopropyl; or
R4 is hydrogen or C1-C4alkyl and R5, R6 and R7 are each hydrogen; or
R4 is hydrogen, methyl or ethyl and R5, R6 and R7 are each hydrogen; or
R4 is hydrogen or methyl and R5, R6 and R7 are each hydrogen; or
R4, R5, R6 and R7 are each hydrogen; or
R8 is C1-C6alkyl; or
R8 is methyl or ethyl; or
R8 is methyl; or
R9, R10, R14, R15, R16, R17 are each independently hydrogen or methyl; or
R9, R10, R14, R15, R16, R17 are each hydrogen; or
X is oxygen, sulfur or xe2x80x94NR8xe2x80x94, wherein R18 is hydrogen or methyl; or
X is oxygen, sulfur or xe2x80x94NHxe2x80x94; or
X is oxygen; or
A is optionally substituted heteroaryl consisting of one or two five to six membered rings containing one to four identical or different heteroatoms selected from oxygen, nitrogen and sulfur; or
A is phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl, benzoxazolyl or quinolyl, each optionally substituted by 1 to 3 substituents selected from C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenyl-C1-C4-alkyl wherein the hydrogens of all the preceding substituents may be in turn optionally substituted by one or several same or different halogens; C1-C8-alkoxy; C3-C8-alkenyloxy; C3-C8-alkynyloxy; C1-C8-alkoxy-C1-C4-alkyl; C1-C8halogenalkoxy; C1-C8-alkylthio; C1-C8-halogenalkylthio; C1-C8-alkylsulfonyl; formyl; C2-C8-alkanoyl; hydroxy; halogen; cyano; nitro; amino; C1-C8-alkylamino; C1-C8-dialkylamino; carboxy; C1-C8-alkoxycarbonyl; C1-C8-alkenyloxycarbonyl or C1-C8-alkynyloxycarbonyl; or
A is phenyl, naphthyl, thienyl, pyridyl, pyrimidinyl, triazinyl or quinolyl, each optionally substituted by 1 to 3 substituents selected from C1-C8-alkyl, C2-C8-alkenyl wherein the hydrogens of all the preceding substituents may be in turn optionally substituted by one or several same or different halogens; C1-C8-alkoxy; C1-C8halogenalkoxy; C1-C8-alkylthio; C1-C8-halogenalkylthio; halogen; cyano; nitro or C1-C8-alkoxycarbonyl; or
A is phenyl or pyridyl, each optionally substituted by 1 to 3 substituents selected from C1-C8-alkyl; C1-C8-haloalkyl; C1-C8-alkoxy; C1-C8halogenalkoxy; C1-C8-alkylthio; C1-C8-halogenalkylthio; halogen; cyano; nitro or C1-C8-alkoxycarbonyl.
Further preferred subgroups of the compounds of formula I are those wherein
R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, or C1-C4alkylsulfonyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12haloalkyl; or a group NR12R13 wherein R12 and R13 are each independently of the other hydrogen or C1-C6-alkyl, or together are tetra- or penta-methylene; and
R2 is hydrogen and R3 is C1-C8alkyl; C1-C8alkyl substituted with hydroxy, mercapto, C1-C4alkoxy or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl; C1-C4alkyl; and
R4 is hydrogen or C1-C4alkyl and R5, R6 and R7 are each hydrogen; or those wherein
n is one; and
R1 is C1-C12alkyl, C2-C12alkenyl; C1-C12haloalkyl; or a group NR12R13 wherein R12 and R13 are each independently of the other hydrogen or C1-C6-alkyl; and
R2 is hydrogen and R3 is C1-C4alkyl; C3-C4alkenyl or cyclopropyl; and
R4 is hydrogen, methyl or ethyl and R5, R6 and R7 are each hydrogen; and
R8 is C1-C6alkyl; or those wherein
n is one; and
R1 is C1-C4alkyl, C2-C4alkenyl; C1-C4haloalkyl; or C1-C2-dialkylamino; and
R2 is hydrogen and R3 is C3-C4alkyl; allyl or cyclopropyl; and
R4 is hydrogen or methyl and R5, R6 and R7 are each hydrogen; and
R8 is methyl or ethyl; or those wherein
n is one; and
R1 is C1-C4alkyl, vinyl; C1-C4haloalkyl; or dimethylamino; and
R2 is hydrogen and R3 is isopropyl; and
R4, R5, R6 and R7 are each hydrogen; and
R8 is methyl.
Amongst the above preferred subgroups of compounds of formula I in turn those are preferred wherein
A is optionally substituted heteroaryl consisting of one or two five to six membered rings containing one to four identical or different heteroatoms selected from oxygen, nitrogen and sulfur; or those wherein
R9, R10, R14, R16, R17 are each independently hydrogen or methyl; and
X is oxygen, sulfur or xe2x80x94NR18xe2x80x94, wherein R18 is hydrogen or methyl; and
A is phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl, benzoxazolyl or quinolyl, each optionally substituted by 1 to 3 substituents selected from C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3xe2x80x94C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenyl-C1-C4-alkyl wherein the hydrogens of all the preceding substituents may be in turn optionally substituted by one or several same or different halogens; C1-C8-alkoxy; C3-C8-alkenyloxy; C3-C8-alkynyloxy; C1-C8-alkoxy-C1-C4-alkyl; C1-C8halogenalkoxy; C1-C8-alkylthio; C1-C8-halogenalkylthio; C1-C8-alkylsulfonyl; formyl; C2-C8-alkanoyl; hydroxy; halogen; cyano; nitro; amino; C1-C8-alkylamino; C1-C8-dialkylamino; carboxy; C1-C8-alkoxycarbonyl; C1-C8-alkenyloxycarbonyl or C1-C8-alkynyloxycarbonyl; or those wherein
R9, R10, R14, R15, R16, R17 are each hydrogen; and
X is oxygen, sulfur or xe2x80x94NHxe2x80x94; or
A is phenyl, naphthyl, thienyl, pyridyl, pyrimidinyl, triazinyl or quinolyl, each optionally substituted by 1 to 3 substituents selected from C1-C8-alkyl, C2-C8-alkenyl wherein the hydrogens of all the preceding substituents may be in turn optionally substituted by one or several same or different halogens; C1-C8-alkoxy; C1-C8halogenalkoxy; C1-C8-alkylthio; C1-C8-halogenalkylthio; halogen; cyano; nitro or C1-C8-alkoxycarbonyl; or those wherein
R9, R10, R14, R15, R16, R17 are each hydrogen; and
X is oxygen; and
A is phenyl or pyridyl, each optionally substituted by 1 to 3 substituents selected from C1-C8-alkyl; C1-C8-haloalkyl; C1-C8-alkoxy; C1-C8halogenalkoxy; C1-C8-alkylthio; C1-C8-halogenalkylthio; halogen; cyano; nitro or C1-C8-alkoxycarbonyl.
Preferred individual compounds are:
(S)-2-ethanesulfonylamino-N-(2-{4-[2-(4-fluoro-phenoxy)-ethoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-methanesulfonylamino-N-(2-{4-[2-(4-fluoro-phenoxy)-ethoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-dimethylaminosulfonylamino-N-(2-{4-[2-(4-fluoro-phenoxy)-ethoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-ethanesulfonylamino-N-(2-{4-[2-(4-fluoro-phenoxy)-ethoxy]-3-methoxy-phenyl}-ethyl)-butyramide,
(S)-2-ethanesulfonylamino-N-(2-{4-[2-(4-fluoro-phenoxy)-ethoxy]-3-methoxy-phenyl}-ethyl)-pentanoylamide,
(S)-2-ethanesulfonylamino-N-(2-{4-[2-phenoxy-ethoxy]-3-methoxy-phenyl}-ethyl)-butyramide,
(S)-2-ethanesulfonylamino-N-(2-{4-[2-(4-chloro-phenoxy)-ethoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-ethanesulfonylamino-N-(2-{4-[2-(3-methyl-phenoxy)-ethoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-ethanesulfonylamino-N-(2-{4-[2-(4-methyl-phenoxy)-ethoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-ethanesulfonylamino-N-(2-{4-[2-(3-fluoro-phenoxy)-ethoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-ethanesulfonylamino-N-(2-{4-[2-(2-chloro-phenoxy)-ethoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-ethanesulfonylamino-N-(2-{4-[1-methyl-2-(4-chloro-phenoxy)-ethoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-methanesulfonylamino-N-(2-{4-[2-(3,4-dichloro-phenoxy)-ethoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-methanesulfonylamino-N-(2-{4-[2-(3-fluoro-phenoxy)-ethoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-methanesulfonylamino-N-(2-{4-[2-(4-chloro-phenylthio)-ethoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-methanesulfonylamino-N-(2-{4-[1-methyl-2-(4-chloro-phenoxy)-ethoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-ethanesulfonylamino-N-(2-{4-[3-(4-chloro-phenyl)-allyloxy]-3-methoxy-phenyl}-ethyl)-2-cyclopropyl-acetamide,
(S)-2-ethanesulfonylamino-N-(2-{4-[2-(4-chloro-phenyl)-allyloxy]-3-methoxy-phenyl}-ethyl)-butyramide,
(S)-2-methanesulfonylamino-N-(2-{4-[2-(4-chloro-phenyl)-allyloxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-ethanesulfonylamino-N-(2-{4-[2-(2-fluoro-phenyl)-allyloxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-methanesulfonylamino-N-(2-{4-[2-(2-fluoro-phenyl)-allyloxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-methanesulfonylamino-N-(2-{4-[2-(4-bromo-phenyl)-allyloxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)(E)-2-ethanesulfonylamino-N-(2-{4-[2-(4-chloro-phenyl)-allyloxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)(Z)-2-ethanesulfonylamino-N-(2-{4-[2-(4-chloro-phenyl)-allyloxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-methanesulfonylamino-N-(2-{4-[2-(4-chloro-phenoxy)-ethoxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide,
(S)-2-ethanesulfonylamino-N-(2-{4-[2-(4-chloro-phenoxy)-ethoxy]-3-methoxy-phenyl}-ethyl)-butyramide,
(S)-2-ethanesulfonylamino-N-(2-{4-[2-(4-chloro-phenoxy)-ethoxy]-3-methoxy-phenyl}-ethyl)-pentanoylamide,
Z-(S)-2-methanesulfonylamino-N-(2-{4-[2-(4-chloro-phenoxy)-allyloxy]-3-methoxy-phenyl}-ethyl)-pentanoylamide, and
Z-(S)-2-ethanesulfonylamino-N-(2-{4-[3-phenoxy-allyloxy]-3-methoxy-phenyl}-ethyl)-3-methyl-butyramide.
Certain xcex1-sulfin- and xcex1-sulfonamino acid derivatives having a different kind of structure have already been proposed for controlling plant-destructive fungi (for example in WO 95/030651, WO 97/14677, WO 98/38160 and WO 98/38161). The action of those preparations is not, however, satisfactory in all aspects of agricultural needs. Surprisingly, with the compound structure of formula I, new kinds of microbicides having a high level of activity have been found.
The xcex1-sulfin- and xcex1-sulfonamino acid amides of formula I may be obtained according to one of the following processes:
a) 
An amino acid of formula II or a carboxy-activated derivative of an amino acid of formula II wherein R1, n, R2 and R3 are as defined for formula I is reacted with an amine of formula III wherein R4, R5, R6, R7, R8, R9, R10 and R11 are as defined above optionally in the presence of a base and optionally in the presence of a diluting agent (step B).
Carboxy-activated derivatives of the amino acid of formula II encompasses all compounds having an activated carboxyl group like an acid halide, such as an acid chloride, like symmetrical or mixed anhydrides, such as mixed anhydrides with O-alkylcarbonates, like activated esters, such as p-nitrophenylesters or N-hydroxysucinimidesters, as well as in situ produced activated forms of the amino acid of formula II by condensating agents, such as dicyclohexylcarbodiimid, carbonyidiimidazol, benzotriazol-1-yloxy-tris(dimethylamino)-phosphonium hexafluorophosphate, O-benzotriazol-1-yl N,N,Nxe2x80x2,Nxe2x80x2-bis(pentamethylene)-uronium hexafluorophosphate, O-benzotriazol-1-yl N,N,Nxe2x80x2,Nxe2x80x2-bis(tetramethylene)uronium hexafluorophosphate, O-benzotriazol-1-yl N,N,Nxe2x80x2,Nxe2x80x2-tetramethyluronium hexafluoro-phosphate or benzotriazol-1-yloxy-tripyrrolidinophosphonium hexafluorophosphate. The mixed anhydrides of the amino acids of the formula II may be prepared by reaction of an amirnio acid of formula II with chloroformic acid esters like chloroformic acid alkylesters, such as ethyl chloroformate or isobutyl chloroformate, optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, n-methyl-piperidine or N-methyl-morpholin.
The present reaction is preferably performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; amides, e.g. N,N-dimethylformamide; nitrites e.g. acetonitrile; or ethers e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or water. It is also possible to use mixtures of these solvents. The reaction is preformed optionally in the presence of an organic or inorganic base like a tertiary amine, e.g. triethylamine, N,N-diisopropyl-ethylamine, pyridine, n-methyl-piperidine or N-methyl-morpholin, like a metal hydroxide or a metal carbonate, preferentially an alkali hydroxide or an alkali carbonate, such as lithium hydroxide, sodium hydroxide or potassium hydroxide at temperatures ranging from xe2x88x9280xc2x0 C. to +150xc2x0 C., preferentially at temperatures ranging from xe2x88x9240xc2x0 C. to +40xc2x0 C.
The compounds of formula II may be prepared by reaction of an amino acid of formula IV where R2 and R3 are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V where R1 and n have the same meanings as defined above and where X is halide, preferentially chlorine or bromine (step A).
The reaction may be performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons, e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or water. It is also possible to use mixtures of these solvents. The reaction is performed optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, n-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide or a metal carbonate, preferentially an alkali hydroxide or an alkali carbonate, such as lithium hydroxide, sodium hydroxide or potassium hydroxide at temperatures ranging from xe2x88x9280xc2x0 C. to +150xc2x0 C., preferentially at temperatures ranging from xe2x88x9240xc2x0 C. to +40xc2x0 C.
b) 
The compounds of formula I may also be prepared by reaction of an amino acid derivative of formula VI wherein R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V wherein R1 and n are as defined for formula I and X is halide, preferentially chlorine or bromine (step C). The reaction is performed in the same manner as described for step A.
c) 
The compounds of formula I may also be prepared by reaction of a phenol of formula VII wherein R1, n, R2, R3, R4, R5, R6, R7 and R8 are as defined for formula I with a compound of formula VIII wherein R9, R10 and R11 are as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate (step D).
The reaction may be performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones e.g. acetone or 2-butanone; esters, e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane, amides, e.g. dimethylformamide, nitrites, e.g. acetonitrile, alcohols, e.g. methanol, ethanol, isopropanol, n-butanol or tert-butanol, sulfoxides e.g. dimethylsulfoxide or water. It is also possible to use mixtures of these solvents. The reaction is performed optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide, a metal carbonate or a metal alkoxide, preferentially an alkali hydroxide, an alkali carbonate or an alkali alkoxide, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide or potassium tert-butoxide at temperatures ranging from xe2x88x9280xc2x0 C. to +200xc2x0 C., preferentially at temperatures ranging from 0xc2x0 C. to +120xc2x0 C.
d) 
The compounds of formula Ia may also be prepared via formula IX wherein R1, n, R2, R3, R4, R5, R6, R7, R8 and A are defined for formula I by reacting of a phenol of formula VII wherein R1, n, R2, R3, R4, R5, R6, R7 and R8 are as defined for formula I with a compound of formula VIIIa wherein R9, R10 and A are as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate (step E).
The reaction is performed in the same manner as described for step D.
The compounds of formula la where R11 is (E) xe2x80x94CHxe2x95x90CHxe2x80x94A and A is as defined for formula I may be prepared by reaction of compounds of formula IX with hydrogen.
The reaction is performed in a solvent like ethers, e.g. diethylether, dioxane or tetrahydrofuran, or like alcohols, e.g. methanol or ethanol, or water in the presence of transition metals or transition metal salts, e.g. nickel, cobalt, palladium, platinium or rhodium, optionally in the presence of bases, e.g. ammonia, or in the presence of salts, e.g. barium sulfate, at temperatures ranging from xe2x88x9220xc2x0 C. to +160xc2x0 C. and at pressures ranging from 1 to 200 bar.
aa) The intermediate amines of formula III may be obtained by one of the following processes: 
Step 1 is the alkylation of a phenol with a compound of formula VIII. The reaction is performed in the same manner as described for procedure c).
Step 2 is the reaction of an aromatic aldehyde with nitromethane. This reaction is performed in a solvent like an organic carboxylic acids, e.g. acetic acidoptionally in the presence of the ammonium salt of this carboxylic acid, e.g. ammonium acetate at temperatures ranging from 0xc2x0 C. to +200xc2x0 C.
Step 3 is the reduction of an unsaturated nitrogen-compound. This reaction is performed in a solvent like an ether, e.g. diethylether, dioxane or tetrahydrofuran, or an alcohol, e.g. methanol, ethanol or isopropanol, with borohydride, with a boron-complex, e.g. the complex of borohydride with tetrahyrofuran, with an alkaliborohydride, with an alkalialuminiumhydride, e.g. lithiumaluminiumhydride, with aluminiumhydride, with an aluminiumalkoxyhydride or with hydrogen optionally in the presence of a transition metal, a transition metal salt or a transition metal complex, e.g. nickel, cobalt, palladium, platinium or rhodium at temperatures ranging from xe2x88x9250xc2x0 C. to +200xc2x0 C.
Step 4 is the reaction of an aldehyde or a ketone of formula with hydroxylamine or with a salt of hydroxylamine. This reaction is performed in a solvent like an alcohol, e.g. methanol, ethanol or isopropanol, like an ether, e.g. diethylether, dioxane or tetrahydrofuran, like an amide, e.g. dimethylformamide, or in water or in a mixture of these solvents optionally in the presence of an organic or inorganic base like a tertiary amine, e.g. triethylamine, like a heterocyclic compound containing nitrogen, e.g. pyridine, or like an alkalicarbonate, e.g. sodium carbonate or potassium carbonate, at temperatures ranging from xe2x88x9220xc2x0 C. to +150xc2x0 C.
Step 5 is the exchange of hydroxy by cyanide. This reaction is performed in an organic solvent like an amide, e.g. dimethylformamide using a metal cyanide like an alkali cyanide, e.g. sodium cyanide or potassium cyanide, at temperatures ranging from 0xc2x0 C. to +200xc2x0 C.
Step 6 is the hydrolysis of an alkyl ester. This reaction is performed in a solvent like an alcohol, e.g. methanol, ethanol or isopropanol, like an ether, e.g. diethylether, dioxane or tetrahydrofuran, like a halogenated hydrocarbon, e.g. dichloromethane, or water or in a mixture of these solvents optionally in the presence of an alkali hydroxide, e.g. lithium hydroxide, sodium hydroxide or potassium hydroxide, or optionally in the presence of an acid, e.g. hydrogen chloride, sulfuric acid or trifluoroacetic acid at temperatures ranging from xe2x88x9220xc2x0 C. to +160xc2x0 C.
Step 7 is the reaction of a carboxylic acid or the activated form of this carboxylic acid with hydrogen azide or an azide-salt. An activated form of a carboxylic acid can be the acid halogenide, e.g. acid chloride, a symmetric or a mixed anhydride. Azide-salts can be alkali azides, e.g. sodium azide. The reaction is performed in a solvent like a hydrocarbon, e.g. toluene or xylene, like a halogenated hydrocarbon, e.g. chloroform, like an ether, e.g. dioxane, like a ketone, e.g. acetone or 2-butanone, like an alcohol, e.g. methanol, ethanol or tert-butanol, or water or in a mixture of these solvents optionally in the presence of an acid like an inorganic acid, e.g. sulfuric acid or hydrogen chloride at temperatures ranging from xe2x88x9240xc2x0 C. to +200xc2x0 C.
In a preferred form the compounds of formula XXVI are prepared starting from compounds of the formula XXV by applying step 5 and step 1 in the same pot.
bb) Amines of formula VI can be obtained by the following process: 
Step 8 is the amidation of an BOC protected amino acid of formula XXI with an amine of formula XXII. The reaction is performed in the same manner as described for step A.
Step 9 is the alkylation of a phenol of formula XXIlII with an compound of formula VIII. The reaction is performed in the same manner as described for step D.
Step 10 is the hydrolysis of a carbamate of formula XIX. The reaction is performed in a solvent like hydrocarbons, e.g. toluene, like halogenated hydrocarbons, e.g. dichloromethane, like ketones, e.g. acetone, like esters, e.g. ethyl acetate, like ethers, e.g. dioxane or tetrahydrofuran, or like water or in mixtures of these solvents optionally in the presence of an organic acid like carboxylic acid, e.g. trifluoroacetic acid, or like a sulfonic acid, e.g. methanesulfonic acid or toluenesulfonic acid, or in the presence of an inorganic acid, e.g. hydrogen chloride or sulfuric acid, at temperatures ranging from xe2x88x9240xc2x0 C. to +160xc2x0 C.
The compounds of formula I are oils or solids at room temperature and are distinguished by valuable microbicidal properties. They can be used in the agricultural sector or related fields preventively and curatively in the control of plant-destructive microorganisms. The compounds of formula I according to the invention are distinguished at low rates of concentration not only by outstanding microbicidal, especially fungicidal, activity but also by being especially well tolerated by plants.
Surprisingly, it has now been found that the compounds of formula I have for practical purposes a very advantageous biocidal spectrum in the control of phytopathogenic micro-organisms, especially fungi. They possess very advantageous curative and preventive properties and are used in the protection of numerous crop plants. With the compounds of formula I it is possible to inhibit or destroy phytopathogenic microorganisms that occur on various crops of useful plants or on parts of such plants (fruit, blossom, leaves, stems, tubers, roots), while parts of the plants which grow later also remain protected, for example, against phytopathogenic fungi.
The novel compounds of formula I prove to be effective against specific genera of the fungus class Fungi imperfecti (e.g. Cercospora), Basidiomycetes (e.g. Puccinia) and Ascomycetes (e.g. Erysiphe and Venturia) and especially against Oomycetes (e.g. Plasmopara, Peronospora, Pythium and Phytophthora). They therefore represent in plant protection a valuable addition to the compositions for controlling phytopathogenic fungi. The compounds of formula I can also be used as dressings for protecting seed (fruit, tubers, grains) and plant cuttings from fungal infections and against phytopathogenic fungi that occur in the soil.
The invention relates also to compositions comprising compounds of formula I as active ingredient, especially plant-protecting compositions, and to the use thereof in the agricultural sector or related fields.
In addition, the present invention includes the preparation of those compositions, wherein the active ingredient is homogeneously mixed with one or more of the substances or groups of substances described herein. Also included is a method of treating plants which is distinguished by the application of the novel compounds of formula I or of the novel compositions.
Target crops to be protected within the scope of this invention comprise, for example, the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucurbitaceae (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamon, camphor) and plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, and also ornamentals.
The compounds of formula I are normally used in the form of compositions and can be applied to the area or plant to be treated simultaneously or in succession with other active ingredients. Those other active ingredients may be fertilisers, micronutrient donors or other preparations that influence plant growth. It is also possible to use selective herbicides or insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of those preparations, if desired together with further carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology.
The compounds of formula I can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities.
Mixing components which are particularly preferred are azoles such as azaconazole, bitertanol, propiconazole, difenoconazole, diniconazole, cyproconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, tebuconazole, tetraconazole, fenbuconazole, metconazole, myclobutanil, perfurazoate, penconazole, bromuconazole, pyrifenox, prochloraz, triadimefon, triadimenol, triflumizole or triticonazole; pyrimidinyl carbinoles such as ancymidol, fenarimol or nuarimol; 2-amino-pyrirridine such as bupirimate, dimethirimol or ethirimol; morpholines such as dodemorph, fenpropidin, fenpropimorph, spiroxamin or tridemorph; anilinopyrimidines such as cyprodinil, pyrimethanil or mepanipyrim; pyrroles such as fenpiclonil or fludioxonil; phenylamides such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace or oxadixyl; benzimidazoles such as benomyl, carbendazim, debacarb, fuberidazole or thiabendazole; dicarboximides such as chlozolinate, dichlozoline, iprodine, myclozoline, procymidone or vinclozolin; carboxamides such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin or thifluzamide; guanidines such as guazatine, dodine or iminoctadine; strobilurines such as azoxystrobin, kresoxim-methyl, metominostrobin, SSF-129, methyl 2-[(2-trifluoromethyl)-pyrid-6-yloxymethyl]-3-methoxyacrylate or 2-[xcex1{[(xcex1-methyl-3-trifluoromethyl-benzyl)imino]-oxy}-o-tolyl]-glyoxylic acid-methylester-O-methyloxime; dithiocarbamates such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb or ziram; N-halomethylthio-dicarboximides such as captafol, captan, dichlofluanid, fluoromide, folpet or tolyfluanid; copper compounds such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper or oxine-copper; nitrophenol derivatives such as dinocap or nitrothal-isopropyl; organo phosphorous derivatives such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos or toclofos-methyl; and other compounds of diverse structures such as acibenzolar-S-methyl, anilazine, blasticidin-S, chinomethionat, chloroneb, chlorothalonil, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone, fenamidone, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, kasugamycin, methasulfocarb, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine or validamycin.
Suitable carriers and surfactants may be solid or liquid and correspond to the substances ordinarily employed in formulation technology, such as e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers. Such carriers and additives are described, for example, in WO 95/30651.
A preferred method of applying a compound of formula I, or an agrochemical composition comprising at least one of those compounds, is application to the foliage (foliar application), the frequency and the rate of application depending upon the risk of infestation by the pathogen in question. The compounds of formula I may also be applied to seed grains (coating) either by impregnating the grains with a liquid formulation of the active ingredient or by coating them with a solid formulation.
The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology, and are for that purpose advantageously formulated in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and by encapsulation in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
Advantageous rates of application are normally from 1 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, especially from 25 g to 750 g a.i./ha. When used as seed dressings, rates of from 0.001 g to 1.0 g of active ingredient per kg of seed are advantageously used.
The formulations, i.e. the compositions, preparations or mixtures comprising the compound(s) (active ingredient(s)) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
Further surfactants customarily used in formulation technology will be known to the person skilled in the art or can be found in the relevant technical literature.
The agrochemical compositions usually comprise 0.01 to 99% by weight, preferably 0.1 to 95% by weight, of a compound of formula I, 99.99 to 1% by weight, preferably 99.9 to 5% by weight, of a solid or liquid adjuvant, and 0 to 25% by weight, preferably 0.1 to 25% by weight, of a surfactant.
Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
The compositions may also comprise further ingredients, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.
The Examples which follow illustrate the invention described above, without limiting the scope thereof in any way. Temperatures are given in degrees Celsius.
Preparation Examples for Compounds of Formula I